Graft copolymers of vinyl benzyl polyglycol ethers and n-vinyl-2-oxazolidinone polymers, improved acrylonitrile polymer compositions obtainable therewith, and method of preparation



amen Patented Jan. 29, 1963 Fire 3,975,947 GRAFT IQPGLYMERSS F VENYLBENZYL POLY- GLYGL ETHERS AND N-ViNYL-Z-GXAZULHDZ- N @NE POLYIVIERS,narnovnn ACRYLUNETRILE PGLYMER COMPQSHIQNS Q B T A I N A B L ETIEREWITH, AND METHQD 01F PREPARATION Stanley A. Murdoch, RanchoCordova, Qaiif, assignor to The Dow Qheinicai Company, Midland, Mich, acorporation of Delaware Fiied ept. 28, 1959, Ser. No. 842,947 19 Ciaims.(tCl. 26i}45.5)

The present invention resides in the general field of organic chemistryand contributes specifically to the polymer art, especially with respectto certain graft copolymer compositions and fiber-forming polymer blendsobtainable therewith. It is particularly concerned with graft copolymersof certain monomeric vinyl benzyl polyglycol ethers that are graftcopolymerized upon or with preformed copolymer substrates ofN-vinyl-Z-oxazolidinones and N-vinyl lactams (hereinafter referred to asVO/VL copolymers), which graft copolymers have especial utility asdye-receptive, antistatic and stabilizing additaments for acrylonitrilepolymer compositions which, advantageously, may be of the fiber-formingvariety.

The invention is also concerned with the compositions that may beobtained by blending the graft copolymers with acrylonitrile polymers,as well as with shaped articles which have been fabricated from suchcompositions and which, as a consequence, have significantly enhancedproperties and characteristics as regards improvements in and relatingto enhanced dye-receptivity, minimized in herent propensity toaccumulate electrostatic charges, natural stability to variousdeteriorating influences, including stability against becomingdeleteriously influenced and degraded upon exposure to heat at elevatedtemperatures and to light.

Within the scope and purview of the invention, there are comprehended(l) the various novel and utile graft copolymers of the indicatedvariety; (2) the advantageous polymer compositions, particularlyfiber-forming compositions, obtained by blending the graft copolymerswith acrylonitrile polymers; (3) various shaped articles fabricated fromand comprised of the graft copolymer-containing acrylonitrile polymercompositions; and (4) methods for the preparation of the above-indicatedcompositions.

It is the main purpose and primary design of the present invention toprovide and make available graft copolymers of certain monomeric vinylbenzyl polyglycol ethers upon preformed VO/VL copolymer substrates thatare especially well suited for being incorporated in acrylonitrilepolymer compositions, particularly compositions of polyacrylonitrile, toserve in the indicated treble capacity of dye-assisting adjuvants,antistatic agents and stabilizing ingredients. It is also a principalaim and chief concern of the invention to provide and make availableacrylonitrile polymer compositions and shaped articles therefrom thatcontain the above-indicated and hereinafter more fully delineated typeof graft copolymeric additaments which compositions have, as intrinsicdistinguishing characteristics, excellent receptivity of andacceptability for any of a wide variety of dyestuffs; permanently imbuedantistatic properties that are unusually good for and not commonlyencountered in polymeric materials of the synthetic, essentiallyhydrophobic varieties of such substances; and efiicacious naturalstability to heat and light, as well as to certain chemical conditions,such as alkaline environments.

The graft copolymers of the present invention which have the indicatedcapacity and utility as additaments for acrylonitrile polymercompositions are comprised of a preformed VO/VL copolymer trunk or baseupon which there is graft copolymerized certain monomeric vinyl benzylpolyglycol ethers of the variety hereinafter described. Advantageously,the graft copolymers may also be prepared from mixtures of thereferred-to monomeric polyglycol ethers with mixtures of certainmonomeric, alkenyl, particularly vinyl, group-containing organicsulfonic acid compounds or derivatives thereof, also hereinafter morefully delineated.

The polymer blend compositions of the present invention which fulfillthe above-indicated ends and offer corollary advantages and benefits,particularly as fiberforming compositions as will hereinafter bemanifest, are, in essence, comprised of an intimate and practicallyinseparable blend, mixture or alloy constitution of (A) an acrylonitrilepolymer that contains in the polymer molecule at least about 80 weightpercent of acrylonitrile, any balance being copolymerized units ofanother ethylenically unsaturated monomeric material that iscopolymerizable With acrylonitrile to provide fiber-formingacrylonitrile polymer products and, most advantageously, ispolyacrylonitrile and (B) a minor proportion of the aboveindicatedvariety of beneficial graft copolymeric addita ment that functions inthe described manner.

The methods of the invention by which the herein con templatedadvantageous compositions may be made in volve preparation of the graftcopolymer, as well as incorporation of a minor proportion of the graftcopolymer product as a beneficial additament in and with theacrylonitrile polymer base by any of several beneficial techniques,hereinafter more thoroughly defined, adapted to suitably accomplish thedesired result.

Without being limited to or by the specific embodiments and modes ofoperation set forth, the invention is illustrated in and by thefollowing didactic exemplifications wherein, unless otherwise indicated,all parts and percentages are to be taken on a weight basis.

ILLUSTRATION A" Into a 500 ml. reactor that is equipped with aneflicient agitator, a nitrogen spar-ger, and a total reflux condenser,

there is charged about 31.5 grams of a copolymer of'N-vinyl-S-methyl-Z-oxazodidinone (VO-M) and N-vinyl- 2-pyrrolidone (VP)copolymerized in a 30:70 respective weight ratio and having aFikentscher K-value of about 30; about 7.2 grams of monomeric1-(2-methoxyethoxy)- 2(vinylbenzyloxy)ethane; about 6.3 grams of sodiumstyrene sulfonate; about 0.5 gram of potassium persulfate; and about181.8 grams of water. The resulting mixture is brought to about pH 6 byacidification with hydrochloric acid (HCl). Under continued nitrogensparging and with continued stirring, the acidified reaction mass ismaintained at a temperature of about 60 C. over a 19-hour period. At theend of this time, the reaction is terminated. About 75.5 percent of themonomers are found to be converted to a graft copolymeric product whichis obtained as white emulsion of the graft copolymer, containing about20 percent of the water-insoluble graft copolymer solids dispersed inwater. Upon analysis, the graft copolymeric product is found to containabout 14 percent of polymerized polyglycol ether monomer units; 11percent of polymerized sodium styrene sulfonate units; and about percentof the VO-M/VP copolymer.

Polyacrylonitrile fibers containing about 10 percent of the abovecopolymer product are prepared by impregnating filamentary structuresthat are in aquagel condition (after having been salt-spun andwet-stretched) in and with an aqueous dispersion of the copolymer thatcontains about 1.5 percent of the graft copolymer solids. Thepolyacrylonitrile aquagel fiber that is employed is obtained byextruding a spinning solution of fiber-forming polyacrylonitrilecomprised of about parts of the polymer dissolved in 90 parts of a 60percent aqueous solution of zinc chloride through a spinnerette having750 individual 6 mil diameter orifices into an aqueous coagulating baththat contains about 43 percent of dissolved zinc chloride to form amultiple filament tow. After being spun, the tow bundle of coagulatedpolyacrylonitrile aquagel fiber is washed substantially free from saltupon being withdrawn from the coagulating bath and then wet-stretchedfor orientation to a total stretched length that is about thirteen timesits original extruded length. The 'aquagel fiber containing about twoparts of water for each part of polymer therein, is then passed throughthe mentioned aqueous impregnating bath of the dissolved copolymeradditive so as to become impregnated therewith to the indicated extent.

Following the impregnation, the aquagel fiber is irreversibly dried at150 C. to destroy the water-hydrated structure and convert it to afinished fiber form. The finally obtained 3 denier fiber product has atenacity of about 4.0 grams per denier, an elongation of about 29percent and a wet yield strength of about 0.90 gram per denier. Thegraft copolymer-containing acrylonitrile polymer fiber product is foundto have excellent natural stability to heat and light as well as againstbecoming degraded under the influence of aqueous alkaline media at pHlevels as high as 10. It is found to be nearly free of propensity toaccumulate charges of static electricity upon handling.

In addition, the graft copolymer-containing sample has good color andhand and is dyeable with all classes of dyestuffs as applied undernormal dyeing conditions.

The fiber product dyes well to deep and level shades of coloration withCalcodur Pink 23L, a direct type of dyestuif (Colour Index Direct Red75, formerly Colour Index 353) and Sevron Brilliant Red 46, a basic dyeformerly known as Basic Red 46 (Colour Index Basic Red 14).

The dyeing with Calcodur Pink 251. is performed at the 4 percent levelaccording to conventional procedure in which the fiber sample ismaintained for about one hour at the boil in the dye bath which containsthe dyestuif in an amount equal to about 4 percent of the Weight of thefiber. The dye bath also contains sodium sulfate in an amount equal toabout percent of the weight of the fiber and has a bath-to-fi-ber weightratio of about 30:1, respectively. After being dyed, the fiber is rinsedthoroughly with water and dried for about minutes at 80 C. Thedye-receptivity of the Calcodur Pink ZBL-dyed fiber is then evaluatedspectrophotometrically by measuring the amount of monochromatic lighthaving a wave length of about 520 millimicrons from a standard sourcethat is reflected from the dyed sample. A numerical value on anarbitrarily designated scale from O to 100 is thereby obtained. Thisvalue represents the relative comparison of the amount of light that isreflected from a standard white tile reflector that has a reflectancevalue of 316 by extrapolation from the 0-100 scale. Lower reflectancevalues are an indication of better dye-receptivity in the fiber. Forexample, a reflectance value of about 20 or to 50 or so foracrylonitrile polymer fibers dyed with 4 percent Calcodur Pink 2BL isgenerally considered by those skilled in the art to be representative ofa degree of dye-receptivity that readily meets or exceeds the mostrigorous practical requirements and is ordinarily assured of receivinggeneral commercial acceptance and approval. The 4 percent Calcodur PinkZBL reflectance value of the graft copolymer-containing fiber product isabout 20.

The antistatic properties of the graft copolymer-containing fiber arethen determined by measuring the electrical conductance of the fiberproduct at various humidities. As is also appreciated by those who areskilled in he a t e as a 5.1 .91 est is hat al fib rs have.

a tendency to generate static electricity upon being handled. Only thosethat are possessed of suificient electrical conductance to dissipate thecharge as quickly as it forms are not hampered by the bothersome effectsof static electricity. Thus, a measure of the electrical conductance ofa fiber is a good indication of its ability to dissipate staticelectricity. The conductivities of the various fiber samples tested arefound by determining their electrical resistances. Resistance, ofcourse, is the reciprocal quantity of conductivity. In order to permitvarious fiber samples to be compared on a common basis, theconductivities of the samples tested are actually measured as volumeresistivities according to the following formula:

Volume Resistivity (Resistance) (Cross-Sectional Area) Path LengthBetween Electrodes to Which Sample Being Tested Is Attached The units ofvolume resistivity are ohm-cm /cm.

Prior to being tested, the graft copolymer-containing polyacrylonitrilefiber prepared in the indicated manner is vat dyed in the conventionalmanner with Cibanone Green BF Dbl. Paste (Colour Index Vat Green No. l).A portion of the vat dyed sample is then subjected to five (5)consecutive No. 3A accelerated wash tests in accordance with theAmerican Association of Textile Chemists and Colorists (AATCC) Manual.The actual resistivities of the merely vat dyed sample as well as thatof the sample that is both vat dyed and scoured are then determined(after the samples being tested are conditioned for seventy-two hours atthe particular temperature and rela tive humidity conditions involved ineach of the tests) by tautly connecting a web-like sample of the yarnbetween two electrodes, each of which are 9 centimeters long spacedparallel 13 centimeters apart, and across which there is applied a 900volt direct current potential.

For purposes of comparison, the volume resistivities of cotton, wool andan unmodified polyacrylonitrile fiber (obtained in the same way as thegraft copolymer-containing fiber but without having the polymericadditament incorporated therein) are also tested in the indicated manneralong with the graft copolymer-containing fiber in accordance with thepresent invention.

The results are set forth in the following tabulation which indicatesthe volume resistivities obtained at various relative humi-dities (RH)at 23 C. of each of the samples tested.

TABLE 1 Volume Resistivz'ties of Various Fiber Samples Compared toPolyacrylonitrile Fibers Impregnaied with Graft Copolymer of MonomericVinyl Benzyl Polyglycol Ether and Sodium Styrene Sulfonate on VO-M/ VPCopolymer Substrate As is apparent in the foregoing, the graftcopolymer-containing sample, even after being severely scoured, haselectrical conductance properties much superior to ordinarypolyacrylonitrile and only slightly poorer than cotton. At the sametime, the physical properties of the copolymer-containing fiber areexcellent, being about equal to those of the unmodifiedpolyacrylonitrile fiber.

ILLUSTRATION B Th8 Procedure of the first illustration is essentiallyrc- Grams Monomer 13.5 30/70 VO-M/VP Copolymer (K-30) 31.5 Water 181.8Potassium persulfate 0.5 pH of charge 6 The resulting product isobtained as a white emulsion that contains about 19.8 percent ofdispersed water-insoluble graft copolymer solids. Conversion of themonomer to graft copolymer is found to be greater than 50 percent. Thegraft copolymer product is comprised of about 20 percent of polymerizedunits of the monomer on the VO-M/VP copolymer substrate.

The procedure of the first illustration is repeated to apply the graftcopolymer product from 1.5 percent aqueous dispersion to apolyacrylonitrile aquagel fiber in order to obtain a fiber productcontaining about percent of the graft copolymeric additamentincorporated therein. The fiber product has excellent dyeability to deepand level shades of coloration with all classes of dyes excepting basictypes. its 4 percent Calcodur Pink 231, reflectance value is about 22.The antistatic properties of the fiber are evaluated as in the firstexample and found to be excellent. As made, the volume resistivities ofthe graft copolymer-containing fiber product are found to be about 7.01O ohm-cmF/cm. at 58 percent RH and about 8.5 X 10 ohm-cmF/cm. at 66percent RH. After a boiling scour, the volume resistivities of the fiberproduct containing the graft copoiymeric additament are found to beabout 1.9 10 ohm-cm. /cm. at 58 percent RH and about 2.3x l0 ohrn-cm.cm. at 66 percent RH. Thus, the antistatic characteristics of the fiberproduct are much better than that of unmodified polyacrylonitrile andcompare quite favorably with wool. its conductivity is not significantlyaltered by the boiling scour. In addition, as is the case with the fiberproduct of the first illustration, the stability to heat and light ofthe graft copolymer-containing fiber product is found to be excellent.

Similar results are also obtained when the foregoing procedure isrepeated excepting to prepare the graft copolymer in a reaction mass inwhich dimethyl sulfoxide is employed as a solvent andazobisisobutyronitrile the catalyst. The graft copolymer prepared in theorganic solvent is separated therefrom and prepared in aqueous emulsionfor purposes of impregnating the acrylonitrile polymer fiber.

Excellent results commensurate with those set forth in the precedingillustrations may also be obtained when the foregoing is repeated toprepare graft copolymer additives from other VO/VL copolymer substrates,such as copolymers of N-vinyl-S-ethyl-2-oxazolidinone and VP; copolymersof N-vinyl-2-oxazolidinone and VP; copolymers of VO-M and N-vinylcaprolactam; copolymers of VO-M and N-vinyl piperidone; and so forth.

Results similar to those set forth in the foregoing can likewise beobtained when the graft copolymer addita ments are incorporated inpolyacrylonitrile and other acrylonitrile polymer fibers to providearticles in accordance with the present invention by blending the graftcopolymer and the fiber-containing acrylonitrile polymer in a spinningcomposition or dope prior to its extrusion into filamentary products byeither wet spinning or dry spinning techniques. In such instances,incidentally, it may be desirable (in order to secure optimum benefit inthe practice of the invention) to employ relatively larger quantities ofthe graft copolymeric additament than when surface impregnation isperformed so that the presence of effective quantities of the additamentat or near the peripheral portion of the article is assured.

The vinyl benzyl polyglycol ether monomers that may be employedindividually or in combination with monomeric organic sulfonic acidcompounds for the preparation of the graft ccpolymeric additaments areof the general formula:

wherein G is selected from the group consisting of alkoxy radicalscontaning from 1 to about 8 carbon atoms (i.e., OCH OC H and other -ORgroups), alkyl sulfide radicals containing from 1 to about 8 carbonatoms i.e., SCH SC H and other -SR radicals) and halogens of atomicnumber 17 to 53 (i.e., chlorine, bromine and iodine); in is the numberof ethylene glycol groups having an average value from about 2 to about40; n is the number of propylene glycol groups that includes 0 and hasan average value that may be as large as about 20 but is never largerthan the value of m, and the sum of the average numerical value of m+nis from about 2 to about 40. In such monomers, the ringsubstituted vinyl(CH=CH radical may be ortho, meta or para on the phenyl nucleus relativeto the benzyl radical. Likewise, the monomeric product may be obtainedin forms of mixtures wherein the vinyl substituent is present on thephenyl nucleus in various positions. The monomeric vinyl benzylpolyglycol ether that is employed may have a molecular weight betweenabout 200 and 2000, advantageously from about 236 to 1200. These vinylbenzyl polyglycol ether monomers and their preparation are furtherdiscussed in the copending application of Stephen C..Stowe for UnitedStates Letters Patent having Serial No. 832,443, filed August 10, 1959',entitled Monomeric Alkenyl Benzyl Polyglycol Ether-s.

The monomeric organic sulfonic acid compounds that may advantageously bemiXed with the monomeric vinyl benzyl polyglycol ethers of Formula I forpreparation of certain of the graft copolymeric products that may beobtained with benefit in the practice of the invention are monomeric,alkenyl group-containing, organic sulfonic acids or derivatives thereofthat are selected from the group of such compounds (including mixturesthereof) consisting of those represented by the formulae:

Yr R

0112:? (CH2) ,,S 03X Z 11) (aromatic organic sulfonic acid compounds) CH=CH(CH S0 X (III) (alkenyl organic sulfonic acid compounds) OH2:(I}-C OO(CHa)nS 0 X z (V) (acryloyl taurine homolog compounds) andCH2=(IJOHiNH-(CH2),,SO X

2 (allyl taurine homolog compounds) Besides those specificallyillustrated herein, other organic sulfonic acids may also be utilizedfor the preparation of the water-insoluble graft copolymers of thepresent invention such, by way of illustration, as those which are setforth in the disclosure of United States Letters Patent No. 2,527,300.In addition to the copolymers specifically described in the foregoingexamples, other water-insoluble copolymeric additarnents that mayadvantageously be employed in the practice of the present inventioninclude graft copolymers on the indicated preformed polymer substratesof the various heretofore delineated monomeric polyglycol ethers withsuch organic sulfonic acids as 2-propene sulfonic acid; sodiumparavinylbenzene sulfonate; 2- and/or 3-sulfopropyl acrylate;a-sulfoacrylic acid; sodium vinyl toluene sulfonate; potassiumorthochlorostyrene sulfonate; Z-hydroxy-S-sulfopropyl acrylate, sodiumsalt; sodium 3-allyloxyl-2Jrydroxypropane sulfonate; 4-sulfophenylacrylate, sodium salt; N-allyl imino di-(Z-ethane sulfonic acid); andthe like.

Still other organic sulfonic acids that may be employed are set forth inthe following representative (but by no means exhaustive) listing,wherein they are grouped according to the above-designated types:

Aromatic alkenyl-containing sulfonic acid compounds (Formula II)-Para-styrene sulfonic acid Grtho-styrene sulfonic acid Para-isopropenylbenzene sulfouic acid Para-vinyl benzyl sulfonic acid Ortho-isopropenylbenzyl sulfonic acid Sodium para-styrene sulfonate Potassiumortho-styrene sulfonate Methyl para-styrene sulfonate Ethyl para-vinylbenzyl sulfonate Ortho-vinyl benzyl sulfonic acid Isopropylortho-isopropenyl benzen sulfonate n-Butyl ortho-styrene sulfonateTertiary butyl para-styrene sulfonate 2-chloro-4-vinyl benzene sulfonicacid 4-bromo-2-isopropenyl benzene sulfonic acid 3-vinyl toluene6-sulfonic acid, sodium salt 2-ethyl-4-vinyl-benzene sulfonic acid2,3-dichloro-4-vinyl benzene sulfonic acid 2,3,5-tribromo-4-vinylbenzene sulfonic acid 2-chloro-3-vinyl-toluene-6-sulfonic acid2,3-diethyl-4-vinyl-benzyl sulfonate, sodium salt kenyl sulfonic acidcompounds (Formula III)- Ethylene sulfonic acid Sodium ethylenesulfonate Potassium ethylene sulfonate Methyl ethylene sulfonateIsopropyl ethylene sulfonate l-propene B-sulfonic acid l-propenel-sulfonic acid, sodium salt l-propene Z-sulfom'c acid, ethyl esterl-butylene 4-sulfonic acid, n-butyl ester l-butylene 3-sulfonic acidTertiary butylene sulfonic acid Sulfoalkylacrylate compounds (Formula IVSulfomethylacrylate 2-sulfoethylacrylate Sulfomethylmethacrylate, sodiumsalt Z-sulfoethylmethacrylate, methyl ester Zsulfoethylmethacrylate,potassium salt Acryl'oyl taurine and homolog compounds (Formula V)-N-acryl-oyl tanrine N-acryloyl tanrine, sodium salt N-methacryloyltaurine, methyl ester N-tmethacryloyl taurine, potassium salt N-acryloyltaurine, ethyl ester N-acryloyl-aminomethane sulfonic acidN-methacryloyl-amin-omethane sulfonic acid, SOdltllIl salt MethylN-methacryloyl-amirromethane sulfonate Allyl taurine and homologcompounds (Formula VI) Allyl tauriue Allyl taurine, sodium salt Allyltaurine, potassium salt Methallyl taurine Methallyl taurine, methylester Meth ly ma ine, i op opyl ester N-allyl-aminomethane sulfonic acidSodium N-allyl-aminomethane sulfonate Lithium N-methallyl-aminomethanesulfonate n-Butyl N-allyl-aminomethane sulfonate The copolymers ofN-vinyl-Z-oxazolidinones (i.e.,VOs) and N-vinyl lactams (i.e., VLs) thatare utilized as prefor ed substrates in the preparation of the graftcopolymeric additaments of the present invention are copolymers of (1)between about 10 and about weight percent, based on the weight of thecopolymer molecule, advantageously between about 40 and 60 weightpercent, of polymerized N-vinyl-Z-oxazolidinone and (2) between about 90and 10 weight percent, based on the weight of the copolymer molecule,advantageously between about 60 and 40 weight percent, of polymerizedN-vinyl lactam. These N-vinyl-Z-oxazolidinone copolymers and theirpreparation are discussed in US. Patents 2,946,772, filed February 27,1958, and 2,948,708, filed April 3, 1958.

The monomeric N-vinyl-Z-oxazolidinons employed for preparation of theVO/VL copolymer substrate are of the general structure:

wherein each R is independently selected from the group consisting ofhydrogen, alkyl radicals, and haloalkyl radicals of from 1 to about 4carbon atoms, and aryl radicals of from 6 to about 10 carbon atoms.Advantageously, ring-substituted N-vinyl-Z-oxazolidinones are employed,particularly those having a single alkyl or aryl substituent in the5-position of the ring such as N-vinyl-5-methyl-2- oxazolidinone(VO-l/l); N-vinyl-S-ethyl-2-oxazolidinone (VO-E);N-vinyl-S-phenyl-2-oxazolidinone (VO-P); and so forth. Of course, ifdesired, non-ring-substituted N-vinyl-2-oxazolidinone may also beemployed.

The N-vinyl lactam monomers that are utilized in the preparation of thepreformed VO/VL copolymer substrates may be any of those (or theirmixtures) which are variously characterized and generically known tothe. art as N-vinyl lactarns or l-vinyl lactams. Such monomers aredisclosed and contemplated in United States Letters Patents Nos.2,265,450; 2,371,804; and2,335,454. Beneficially, the N-yinyl lactamsthat are employed are N-vinyl- 2-pyrrolidone (VP), also known asN-vinyl-2-pyrrolidi-. none; N-vinyl-piperidone (VPip); N-vinylcaprolactam (VC); N-vinyl-S-methyl-Z-pyrrolidone (VP-.M); and the like,particularly VP.

It is desirable for the VO/VL copolymer that is used to be awater-soluble material. In cases where certain ring-substituted VOs areemployed, such as VO-M, VO-E and VO-P, it is generally beneficial forthe copolymer to contain at least about 40 Weight percent of the VL co.-polymerized therein. Copolymers having substantially less VL may tend towater-insolubility and make it neces-. sary to work with a product thatmay have a cloud (or precipitation) point in water or other aqueoussolution beneath the boil. Copolymers containing from about 10. to about30 weight percent VO are generally water-. soluble at normal roomtemperatures (i.e., 20-25 C.) at solution concentrations as great as20430 weight percent, and frequently greater. w

The graft copolymers of the present invention may gen. erally beprepared by methods of polymerization, such as those which have beendemonstrated in the foregoing illustrative examples, that employ suchpolymerization catalysts as persulfates, organic and inorganic peroxide9 and azo type materials (such as azobisisobutyronitrile) in quantitiesthat are conventional for such uses. The graft copolymers may oftentimesbe prepared by polymerizing the monomeric constituent onto the preformedcopolymer substrate under the influence of high energy irradiation suchas by means of X-rays and the like. The graft copolymers may be preparedin both aqueous and organic solvent vehicles using temperatures for thedesired polymerization that may vary from about room temperature to theboiling point of the polymerization mixture. It is ordinarilysatisfactory to conduct the reaction at a temperature of about 50 to 80or 100 C. Usually, depend ing on the specific factors that may beinvolved, the graft copolymerization may be accomplished satisfactorilywithln a time period of about 10 to 60 hours.

The compositions of the graft copolymeric additaments that are employedcan vary within relatively wide limits. The content of the monomericconstituent, Whether it is the monomeric vinyl benzyl polyglycol etherbeing individually employed or in combination with the monomeric organicsulfonic acid compounds, may advantageously be between about 20 and 80percent by weight of a graft copolymer, with the preformed copolymersubstrate consisting of the remaining 80 to 20 percent of the polymericproduct. In many cases, especially to secure optimum dye-receptivity,nearly equivalent or about commensurate proportions of the graftcopolymerized monomeric constituent and the preformed copolymersubstrate upon which it is graft copolymerized may be employed for thepreparation of the graft copolymeric additaments. When the monomericvinyl benzyl polyglycol ether is employed in mixtures with monomericorganic sulfonic acid compounds for preparation of the graft copolymerprod ucts, either of the diverse type of monomers may be present in themixture in proportions of from about 10 to 90, advantageously from about30 to 70 mole percent of either monomer. Thus, a mixture of a vinylbenzyl polyglycol ether monomer with an organic sulfonic acid monomercan advantageously contain from 10 to 90 mole percent of the former withthe balance of the monomeric mixture consisting of the monomericsulfonic acid compound.

The polymerization system that is employed for the preparation of thegraft copolymers used in the present invention may consist of as much as50 weight percent of the monomers to be polymerized in the aqueous orother medium. The amount of polymerizable constituents that are providedin the copolymerization system may be influenced somewhat by the mannerin which it is intended to incorporate the product in the syntheticpolymer compositions in order to provide the compositions of theinvention.

If, for example, it is intended to incorporate the graft copolymerproducts by blending into a fiber-forming composition prior to itsfabrication into shaped articles, the graft copolymerization system may,if desired, contain about equal proportions by Weight of the chargedpolymerizable constituents and the polymerization medium. whichpreferably is miscible with and tolerable in the spinning solutionsolvent being used. In such cases, the graft copolymer product mayordinarily be obtained as an easily dispersed gel that, after beingdried and isolated from unreacted monomer, may readily be directlyincorporated in the fiber-forming composition.

If the incorporation of the graft copolymeric additament in afiber-forming composition is to be achieved by impregnation therewith ofan already-formed shaped article of the composition, it may be desirableto effect the polymerization so as to directly form the polymerizationsystem as a suitable applicating emulsion or suspension of the graftcopolymeric product, or as a solution when sufiiciently hydrophilicpolyglycol constituents are present in the monomeric vinyl benzylpolyglycol ether employed- For such purposes, the polymerization systemmay be:

prepared to contain as little as 5 or 10 percent by weight of thepolymerizable monomeric and polymeric ingredients. Preferably, if thegraft copolymer is water-insoluble, such a polymerization may beconducted under the influence of vigorous agitation to facilitatepreparation of an emulsified or thoroughly dispersed product. It mayalso be beneficial under such circumstances to incorporate a dispersantor emulsifying agent in the polymerization system to facilitateobtaining a stable and homogeneous emulsi'fied product. Such a methodfor preparing the graft copolymeric aditaments that are employed in thepresent invention may be especially appropriate when they are intendedto be applied to acrylonitrile polymer fibers and the like that arederived from aquagels in the course of their manufacture, such as theacrylonitrile polymer fibers that are wet spun from aqueous salinesolutions of the fiber-forming polymer.

In such instances, as has been demonstrated, the emulsified, graftcopolymeric additaments may be impregnated into the fiber while it is ina swollen or gel condition, as an acrylonitrile polymer fiber in anaquagel condition, in order to obtain the desired copolymer-containingproduct. A dissolved, water-soluble product may be similarlyimpregnated.

In this connection, when it is desired to blend the graft copolymericadditament in a synthetic polymer fiberforming solution prior to itsextrusion, such as an aqueous saline acrylonitrile polymer solution, awater-insoluble graft copolymer may be physically reduced by comminutionto a sufiiciently fine state to permit its dispersion in spinnablecondition throughout the blended spinning solution in the solvent if itis otherwise insoluble in the solvent. While this may be accomplished bydiverse techniques, it is generally advantageous to comminute the graftcopolymer in the presence of the non-dissolving solvent, such as anaqueous saline acrylonitrile polymer spinning solution. Thus, if theaqueous saline polyacryloni trile solvent that is being employed is anaqueous solution of zinc chloride, or its equivalent, that contains atleast about 55 percent and preferably about 60 percent by weight ofdissolved zinc chloride, it may be advantageous to comrninute awater-insoluble graft copolymeric additament while it isin a mixturewith the saline solvent solution that contains between about 5 and 10percent by weight of the copolymer. Analogous procedures may be employedwhen other solvents are involved. Ball or rod mills or other attritionapparatus may be employed beneficially for the comminution. It isgenerally beneficial under such circumstances to avoid the use of ballsor rods that are made of metal since they may contaminate the product,especially when aqueous saline solvents are utilized. Porcelain or otherceramic parts may usually be employed with advantage. A stablesuspension of a water-insoluble graft copolymeric additament in theacrylonitrile polymer solvent that is suitable for blending in thespinning solution of the acrylonitrile polymer to provide a spinnablecomposition may usually be obtained by milling the mixture of graftcopolymeric additament and solvent for an extended period that mayexceed hours. The suspension that is thereby obtained may then bedirectly blended in the proper proportions with the acrylonitrilepolymer spinning solution to provide a composition in accordance withthe present invention.

If desired, the graft copolymer-containing acrylonitrile polymercompositions may comprise as much as 20 or more percent by weig t of thegraft copolymeric additament, based on the weight of the composition.Usually, however, suitable properties and characteristics and betterfiber-forming properties in a given composition may be achieved whenlesser proportions of the graft copolymeric additament are incorporatedtherein. An appreciable improvement in dye-receptivity, anti-static properties and stability may frequently be obtained when a quantity of thegraft copolymeric additament that is as small as 2 (and even as low as 1or less) percent by Weight is employed. Advantageously, an amountbetween. about 4 and percent by weight of the graft copolymericadditament may thus be utilized in the composition. Greater advantagesmay often accrue when the amount of the graft copolymeric additamentthat is incorporated in the composition is in the neighborhood of 5-l0percent by weight, based on the weight of the composition.

, As has been indicated, the graft copolymeric additaments may beincorporated in the acrylonitrile polymer compositions according tovarious techniques. Thus, for example, the graft copolymeric additarnentand the acrylonitrile polymer may be directly blended in order toprovide the composition which, incidentally, may be used for any desiredfabrication purpose in addition to fiber-forming and the like.Beneficially, the polymers may be comminuted, either separately or incombination, before being intimately blended together by mechanical orother means. The blended polymers may be prepared into suitablefiber-forming systems by dissolving or otherwise dispersing them in asuitable liquid medium. 01', the compositions may be provided infiber-forming system by sequentially dispersing the polymers in anydesired order. in a suitable medium, as by incorporating the graftcopolymeric additament in a prepared, acrylonitrile ipolymer spinningsolution, dope, or the like.

As is evident from the exemplifying illustrations heretofore. included,a highly. advantageous technique for providing the compositions,particularly when ac'rylonitrile. polymer fiber products are involved,is to apply or impregnate the graft copolymeric additament from anaqueous dispersion thereof to a shaped acrylonitrile polymer article,that is in an aquagel condition in a known inanner. Thus, anacrylonitrile polymer filamentary article that has been spun from anequeous saline spin ning solution may be conveniently passed, after itscoagulation and while it is in an aquagel condition, through afwaterbath containing the dissolved graft copolymeric additament in order toimpregnate the filament with the graft copolymer and provide acomposition and an article in accordance with the invention. Inaddition, in situ polymerization techniques may also be relied upon toprovide the graft copolymeric additament in the acryl onitrile polymersin either fabricated or unfabricated form.

he compositions of the invention may advantageously be utilized in orwith fiber-forming systems of any desired-type inorder to provide fibersand the like according to procedures and techniques that areconventionally employed for's'uch purposes in the preparation of'fibers'andsuch related shaped articles as filaments, strands, yarns, tows,threads, cords and other funicular structures, ribbons, tapes, filrns,foils, sheets and the like which may be manufactured from syntheticpolymeric materials. It is frequently desirable to employ concentratedsolutions of salts or mixtures of salts as the dispersing or dissolvingmedia for such purposes. Such solutions 331, as has been indicated,contain at least about 55' percent by weight, based on the weight of thesolution, of zinc chloride or other knownsaline solvents for thepolyrner. Acrylonitrile polymer fiber products that are spun from salinefiber-forming systems may, by way. of further illustration, becoagulated in more dilute saline solutions of a like or similar natureand may then be processed after coagulation according to conventionaltechniques of washing, stretching, drying, finishing and the like withthe modification of the present invention being accomplished prior orsubsequent to the spinning as may be desired and suitable in particularinstances.

The acrylonitrile polymer fiber products in accordance with the presentinvention (one of which is schematisa y llus ra ed n the sale figure t hom n n drawing) have excellent physical properties and other desirablecharacteristics for a textile material and have a high capacity for andare readily and satisfactorily dyeable to deep and level shades with anyof a Wide variety of dyestuiis. For example, they may be easily andsuccessfully dyed according to conventional procedures using acid, vat,acetate, direct'naphthol and sulfur dyes.

Such dyestufis, by way of didactic illustration, as Calcocid AlizarineViolet (Colour Index 61710, formerly Colour Index 1080), SulfanthreneRed 313 (Colour Index Vat Violet 2), Amacel Scarlet GB (Colour IndexDirect Red 1 also known as Arnacel Scarlet BS, and having AmericanPrototype Number 244), Calcodur Pink 2BL (Colour Index 353, also morerecently, Colour Index Direct Red Naphthol ASMX (Colour Index 35527),Fast Red TRN Salt (Colour Index Azoic Diazo Component l1), and ImmedialBordeaux G (Colour Index Sulfur Brown 12) may advantageously be employedfor such purposes.

Other. dyestuifs, by way of further illustration, that may be, utilizedbeneficially on the graft copolymercontaining acrylonitrilev polymerblended fiber products of the. invention include such direct cotton dyesas Chlorantine Fast Green SELL (Colour Index Direct Green 2.7),Chlorantine Fast Red 7B (Colour Index Direct Red 811)., Pontamine GreenGX Gene. percent (Colour Index Direct Green 6), Calcomine Black EXNConc. (Colour Index Direct Black 38), Niagara Blue NR (Colour IndexDirect Blue 151) and Erie Fast Scarlet 43A (Colour Index Direct Red'24);such acid dyes asAnthraquinone Green GN' (Colour Index Acid Green- 25),SulfonineBrown 2R (Colour Index Acid Orange 51), Sulfonine 1 Yellow 26(Colour Index Acid Yellow 40), Xylene Milling Black 23 (Colour IndexAcid Black 26A), Xylene Milling Blue FF (Colour Index Acid Blue 6 l-),Xylene Fast Rubine 3GB PAT (Colour Index Acid Red 57), Calcocid NavyBlue R Conc. (Colour Index Acid 1'20), Calcocid Fast Blue BL (ColourIndex Fast Blue 59 Calcocid Milling Red 3R (Colour Index Bed 151;), Alizarine Levelling Blue 2R (Colour Index Acid Blue 51), Am-acid Azo YellowG Extra (Colour Index Acid Yellow 63); such mordant-acid dyesasAlizarine Light Green GS (Colour Index Acid Green 25); such basic dyesas Brilliant Green Crystals (Colour Index Basic Green I), and RhodarnineB Extra S (Colour Index Vat Blue 3 5); such vat dyestuffs as Midland VatBlue R Powder (Colour Index Vat Blue 35.), Sulfanthrene Brown G Paste.(Colour Index Vat Brown 5), Sulfanthrene Blue 23 Dbl. paste (ColourIndex. Vat Blue 5), and Sulfanthrene Red 33 Paste (Colour Index VatViolet 2); various soluble vat dyestutfs; such acetate dyes as CellitonPast Brown BRA Extra CF (Colour Index Dispersed Orange 5), Celliton EastRubine BACF (Colour Index Dispersed Red 13), Ar'tisil DirectRed SBP. andCelanthrene Red 3BN Conc. (-Both Colour Index Dispersed Red- 15),Cel-anthrene Pure Blue BRS 400-. percent (Colour Index Dispersed Blue 1)and Acetamine Yellow N (Colour Index Dis-- persed Yellow 32) B-Naphthol-2-chloro:4-nitroaniline, an azoic dye; suchsulfur dyes as. KatigenBrilliantBlue GGS-High Cone. (Colour Index S ulf. Blue 9) and IndoCarbon CLGS (Colour IndexSulf. Blue 6); and various l '5 i ?l Y $i9f S-The clye d products are generally lightfast and stable to heat and arewell imbued with a good resistance to clrocking. In addition, the dyedproducts exhibit good washfastness and retain the dye-assisting graftcopolymeric additament in a substantially. permanent manner, despiterepeated. exposure. and subjection to washing, laundering anddry-cleaning treatments.

Whatis 'clairnedis: l. 'Graft copolymer of between about 20 and aboutcnFwOonm'onioHnmwononaonnuo wherein G is selected from the groupconsisting of alkoxy radicals containing from 1 to about 8 carbon atoms;alky'l sulfide radicals containing from 1 to about 8 carbon atoms andhalogens of atomic number 17 to 53; m has an average value from about 2to about 40; n has an average value of from to about 20 with thelimitation that the value of n is always less than that of m and the sumtotal of m plus n is from about 2 to about 40; and (b) from about 80 toabout 20 weight percent of a copolymer of a N-vinyl-Z-oxazolidinone anda N-vinyl lactam, said copolymer being from about to about 90 weightpercent, based on copolymer weight, of a N-vinyl-Z-oxazolidinone monomercopolymerized with from about 90 to about 10 weight percent, based oncopolymer weight, of a N-vinyl lactam monomer.

2. The graft copolymer of claim 1, containing, in polymerized form, thepolymer molecule between about 30 and about 50 weight percent of saidmonomer as graft copolymerized substituents on said N-vinyl-2-oxazolidinone N-vinyl lactam copolymer substrate.

3. The graft copolymer of claim 1, wherein said copolymer is a copolymerof N-vinyl-S-methyl-Z-oxazolidinone and N-vinyl-Z-pyrrolidone.

4. Graft copolymer of between about and about 80 weight percent of (a) amixture of monomers consisting of from about 10 to about 90 mole percentof ('1) Va monomeric vinyl benzyl'polyglycol ether of the formulawherein G is selected from the group consisting of alkoxy radicalscontaining from 1 to about 8 carbon atoms; alkyl sulfide radicalscontaining from 1 to about 8 carbon atoms and halogens of atomic number1.7 to 53; m has an average value from about 2 to about 40; n has anaverage value of from 0 to about 20 with the limitation that the valueof n is always less than that of m and the sum total of in plus n isfrom about 2 to about .40; and. (2) from about 90 to. about 10 molepercent of an alkenyl group-containing organic'sulfonic acid compoundselected from the group represented by the formulae:

Y, am

about 20 weight percent of a copolymer of a N-viny1-2-- oxazolidinoneand a N-vinyl lactam, said copolymer being from about 10 to about 90weight percent, based on copolymer weight, of a N-vinyl-2 oxazo1idinoneconsisting of those group consisting of 1'4 monomer copolymerized withfrom about '90 to about 10 weight percent, based on copolymer weight, ofa N-vinyl lactam monomer.

5. Method for the preparation of a graft copolymer which comprisespolymerizing between about 20 and about weight percent, based onresulting graft copolymer weight, of a monomeric vinyl benzyl polyglycolether having the formula:

of n is always less than that of m and the sum total of in plus it isfrom about 2 to about 40; with between about 80 and about 20 weightpercent of a copolymer of a N- vinyl-2-oxazolidinone and a N-vinyllactam, said copolymer being from about 10 to about weight percent,based on copolymer weight, of a N-vinyl-2-oxazolidin0ne monomercopolymerized with from about 90 to about 10 weight percent, based oncopolymer weight, of a N-vinyl lactam monomer.

6. Method for the preparation of a graft copolymer which comprisespolymerizing between about 20 and about 80 weight percent, based onresulting graft copolymer weight, of (a) a mixture of monomersconsisting of from about 10 to about 90 mole percent of (l) a monomericvinyl benzyl polyglycol ether of the formula:

(I) wherein G is selected from the group consisting of alkoxy radicalscontaining from 1 to about 8 carbon atoms, alkyl sulfide radicalscontaining from 1 to about 8 carbon atoms and halogens of atomic number17 to 53; m has an average value from about 2 to about 40; n has anaverage value of from 0 to about 20 with the limitation that the valueof n is always less than that of m and the sum total of m'plus n is fromabout 2 to about 40; and (2) from about 90 to 10 mole percent of analkenyl group-containing organic sulfonic acid compound from the groupconsisting of those having the formulae:

integer from 1 to 4; with (b) between about 80 and about 20 weightpercent of a copolymer of a N-vinyl-Z-oxazolidinone and a N-vinyllactam, said copolymer being from about 10 to about 90 weight percent,based on copolymer weight, of an N-vinyl-2-oxazolidinone monomercopolymerized with from about 90 to about 10 weight percent, based oncopolymer weight, of a N-vinyl lactam monomer.

7. Composition comprising a major proportion of at least about 80 weightpercent, based on composition weight, of (A) a polymerized ethylenicallyunsaturated monomeric material containing at least about 80 weightpercent of polymerized acrylonitrile, and (B) a minor proportion of upto about 20 weight percent, based on composition weight, of a graftcopolymer of (a) from about 20 to about 80 weight percent of a monomericvinyl benzyl polyglycol ether having the formula:

wherein G is selected from the group consisting of alkoxy radicalscontaining from 1 to about 8 carbon atoms; alkyl sulfide radicalscontaining from 1 to about 8 carbon atoms and halogens of atomic number17 to 53; m has an average value from about 2 to about 40; n has anaverage value of from to about 20 with the limitation that the value ofn is always less than that of m and the sum total;

of m plus it is from about 2 to about 40; and (b), between about 80 andabout 20 weight percent of a copolymer of an N-vinyl-2oxazolidinone andan N-vinyl lactam, said copolymer being from about to about 90 weightpercent, based on copolymer weight, of an N-vinyl-Z-oxae zolidinonemonomer copolymerized with from about 90 to about 10 weight percent,based on copolymer weight, of an N-vinyl lactam monomer.-

8. The composition of claim 7 containing between about 4 and aboutweight percent, based on composition weight, of said graft copolymer.

9. The composition of claim 7, wherein the graft copolymer is of amonomer of said Formula I wherein m is 2 and n is O and a copolymer ofN-vinyl-S-methyl-Z- oxazolidinone and N-vinyl-Z-pyrrolidone.

19. The composition of claim 7, wherein the graft copolymer is of amonomer of said Formula I wherein m is 15 and n is 0 and a copolymer ofN-vinyl-S-rnethyl-Z- oxazolidinone and N-vinyl-Z-pyrrolidone.

11. The composition of claim 7, wherein the graft copolymer is of amonomer of said Formula I wherein m is and n is 2 and a copolymer ofN-vinyl-S-methyl-Z- oxazolidinone and N-vinyl-Z-pyrrolidone.

12. The composition of claim 7, wherein the acrylonitrile polymer ispolyacrylonitrile.

13. The composition of claim 7-, dispersed in a solvent forpolyacrylonitrile.

14. A filamentary shaped article having the composition set forth inclaim 7.

l5. Composition comprising a major proportion of at least about 80weight percent, based on composition weight, of (A) a polymerizedethylenically unsaturated monomeric material containing at least about80 weight percent of polymerized acrylonitrile, and (B) a minorproportion of up to about 20 weight percent, based on compositionweight, of a. graft copolymer; of (a) from about 20 to about 80 weightpercent of a mixture of monomers consisting of (.1) from about 10 toabout 90 mole percent of a monomeric vinyl benzyl polyglycol ether ofthe formula:

on,=on -ormoornout)... oouomoiso ro nyl group-containing organicsulfonic acid compound selected from the group consisting of thosehaving the formulae:

all wherein X is selected from the group consisting of hydrogen,aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms andalkali metals; Y is selected from the group consisting of hydrogen,chlorine and bromine; R is selected from, the group consisting of methyland ethyl; Z is selected from the group consisting of hydrogen andmethyl, m is, an integer from 0 to 2; nis an integer from 1. to 2;,p isan integer from O tol; and r is an integer froml to 4; and.(,b),between. about and 20 weight percent of a copolymer ofa N-vinyl-Z-oxazolidinone and. a N-vinyl lactam, said copolymer being from about 10to about weight percent, based on. copolymer weight, of, aN-vinyl-Z-oxazolidinone monomer copolymerized with from about 90 toabout 10- wei'ght percent, based on copolymer weight, of a N-vinyl;lactam monomer.

16. Method for thepreparationot' a dye-receptive, antistatic, stable tolight and heat, synthetic, linear, hydro phobic polymer compositionwhich comprises mixing together a minor proportion of up to about 20weight percent, based on composition weight, of (B) a graft copolymerof- (a) from about 20 to about 80 weight percent of a monomeric vinylbenzyl polyglycol ether of the formula:

wherein G is selected from the group consisting of alkoxy radicalscontaining from 1 to, about 8 carbon atoms; alkyl sulfide radicalscontaining from 1, to about 8 carbon atoms and halogens of atomic number17 to 53; m has an average value from about; 2 to about 40; n has anaverage value of from G to about 20 with the limitation that thevaluesot n is always-less thau that of m and the sum total of m plus itis from about 2 to about 40; and (b), between about 80 and about 20weight percent of a copolymer of a N-vinyl-2=oxazolidinone and a N-vinyl lactam, said copolymer being from about 10 to about 90 weightpercent, based on copolymer Weight, of a NWinyl-Z-oxazolidinone, monomercopolymerized with from about 90 to about 10 weight percent, based oncopolymer weight, of a N-vinyl lactam monomer; with (A) a polymerizedethylenically unsaturated monomeric material containing at least about80 weight percent of polymerized acrylonitrile.

17. Method for the preparation of a dye-receptive, antistatic, stable tolight and heat, synthetic, linear, hydrophobic polymer composition whichcomprises mixing together a minor proportion of up to about 20 weightper cent, based on composition weight, of (B) a graft copolymer of (a).from about 20 to about 80 weight percentof a mixture of monomersconsisting of (1) from about 10 to about 90 mole percent of a monomericvinyl benzyl polyglycol ether of the formula:

wherein G is selected from the group consisting of alkoXy radicalscontaining from 1 to about 8 carbon atoms; alkyl sulfide radicalscontaining from 1 to about 8 carbon atoms and halogens of atomic number17 to 53; m has an average value from about 2 to about 40; n has anaverage value of from to about 20 with the limitation that the value ofn is always less than that of m and the sum total of in plus n is fromabout 2 to about 40; and (2) from about 90 to about mole percent of analkenyl group-containing organic sulfonic acid selected from the groupconsisting of those having the formulae:

all wherein X is selected from the group consisting of hydrogen,aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms andalkali metals; Y is selected from the group consisting of hydrogen,chlorine and bromine; R is selected from the group consisting of methyland ethyl; Z is selected from the group consisting of hydrogen andmethyl, m is an integer from 0 to 2, n is an integer from 1 to 2; p isan integer from 0 to 1; and r is an integer from 1 to 4; and ([1),between about 80 and about 20 weight percent of a copolymer of aN-vinyl-Z- oxazolidinone and a N-vinyl lactam, said copolymer being fromabout 10 to about 90 weight percent, based on copolymer weight, of aN-vinyl-2-oxazolidinone monomer copolymerized with from about 90 toabout 10 weight percent, based on copolymer weight, of a N-vinyl lactammonomer; with (A) a polymerized ethylenically unsaturated monomericmaterial containing at least about 80 weight percent of polymerizedacrylonitrile.

18. Method for the preparation of a dye-receptive antistatic, stable tolight and heat, synthetic, linear, hydrophobic polymer composition whichcomprises immersing an aquagel of a polymerized ethylenicallyunsaturated monomeric material containing at least about 80 weightpercent of polymerized acrylonitrile in the form of a shaped articleinto an aqueous dispersion of a graft copolymer of (a) from about 20 toabout 80 weight percent of a monomeric vinyl benzyl polyglycol ether ofthe formula:

om=on-omwomo11smw CHCHaCHz) no wherein G is selected from the groupconsisting of alkoxy radicals containing from 1 to about 8 carbon atoms;alkyl sulfide radicals containing from 1 to about 8 carbon atoms andhalogens of atomic number 17 to 53; in has an average value from about 2to about 40; n has an average value of from 0 to about 20 with thelimitation that the value of n is always less than that of m and the sumtotal of m plus n is from about 2 to about 40; and (b), between about 80and about 20 weight percent of a copolymer of a N-vinyl-2-oxazolidinoneand a N-vinyl lactam, said copolymer being from about 10 to about 90weight percent, based on copolymer weight, of a N-vinyl-2-oxazolidinonemonomer copolymerized with from about 90 to about 10 Weight percent,based on copolymer weight, of a N-vinyl lactam monomer until betweenabout 2 and about 20 weight percent of said graft copolymer, based onresulting dry composition weight, is incorporated in said aquage'l; anddrying said graft copolymer-containing aquagel to convert it from theaquagel condition to a finished shaped article form.

19. Method for the preparation of a dye-receptive, antistatic, stable tolight and heat, synthetic, linear hydrophobic polymer composition whichcomprises immersing an aquagel of a polymerized ethylenicallyunsaturated monomeric material containing at least about weight percentof polymerized acrylonitrile in the form of a shaped article into anaqueous dispersion of a graft copolymer of (a) from about 20 to about 80weight percent of a mixture of monomers consisting of (1) from about 10to about mole percent of a monomeric vinyl benzyl polyglycol ether ofthe formula:

om=on- 3ona o onlounmto onon onnne (I) wherein G is selected from thegroup consisting of alkoxy radicals containing from 1 to about 8 carbonatoms; alkyl sulfide radicals containing from 1 to about 8 carbon atomsand halogens of atomic number 17 to 53; m has an average value fromabout 2 to about 40; n has an average value of from 0 to about 20 withthe limitation that the value of n is always less than that of m and thesum total of in plus n is from about 2 to about 40; and (2) from about90 to about 10 mole percent of an monomeric alkenyl group-containingorganic sulfonic acid compound selected from the group consisting ofthose having the formulae:

all wherein X is selected from the group consisting of hydrogen,aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms andalkali metals; Y is selected from the group consisting of hydrogen,chlorine and bromine; R is selected from the group consisting of methyland ethyl; Z is selected from the group consisting of hydrogen andmethyl, m is an integer from 0 to 2; n is an integer from 1 to 2; p isan integer from 0 to l; and r is an integer from 1 to 4; and (b),between about 8'0 and about 20 weight percent of a copolymer of aN-vinyl-2-oxazolidinone and a N-vinyl lactam, said copolymer being fromabout 10 to about 90 weight percent, based on copolymer weight, of aN-vinyl-2- oxazolidinone monomer copolymerized with from about 90 toabout 10 weight percent, based on copolymer weight, of a N-vinyl lactammonomer until between about 2 and about 20 weight percent of said graftcopolymer, based on resulting dry composition weight, is incorporated insaid aquagel, and drying said graft copolymercontaining aquagel toconvert it from the aquagel condittion to a finished shaped articleform.

Cresswell July 3, 1951 Tousignant et a1 Nov. 18, 1958 UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,075,947 V January29 1963 Stanley A. Murdock certified that err ection and that th It ishereby ent requiring corr or appears in the corrected below.

above numbered pate said Letters Pat ent should read as(sulfoalkylacrylate organic sulfonic acid compounds) Signed and sealedthis 31st day of December 1963.

EAL l t testz EDWIN ,L. REYNOLDS ERNEST w. SWIDER Attesting Officer AC ti ng Commissioner of Patents

15. COMPOSITION COMPRISING A MAJOR PROPORTION OF AT LEAST ABOUT 80WEIGHT PERCENT, BASED ON COMPOSITION WEIGHT, OF (A) A POLYMERIZEDETHYLENICALLY UNSATURATED MONOMERIC MATERIAL CONTAINING AT LEAST ABOUT80 WEIGHT PERCENT OF POLYMERIZED ACRYLONITRILE, AND (B) A MINORPROPORTION OF UP TO ABOUT 20 WEIGHT PERCENT, BASED ON COMPOSITIONWEIGHT, OF A GRAFT COPOLYMER OF (A) FROM ABOUT 20 TO ABOUT 80 WEIGHTPERCENT OF A MIXTURE OF MONOMERS CONSISTING OF (1) FROM ABOUT 10 TOABOUT 90 MOLE PERCENT OF A MONOMERIC VINYL BENZYL POLYGLYCOL ETHER OFTHE FORMULA: